Decontamination of Cr(VI) facilitated formation of persistent free radicals on rice husk derived biochar

PFRs were produced on biochar during Cr(VI) decontamination. PFRs formation on biochar was owing to the oxidization of phenolic-OH by Cr(VI). Appearance of excessive oxidant led to the consumption of PFRs on biochar. Biochar charred at high temperature possessed great performance to Cr(VI) removal. This study investigated the facilitation of Cr(VI) decontamination to the formation of persistent free radicals (PFRs) on rice husk derived biochar. It was found that Cr(VI) remediation by biochar facilitated the production of PFRs, which increased with the concentration of treated Cr(VI). However, excessive Cr(VI) would induce their decay. Biochar with high pyrolysis temperature possessed great performance to Cr(VI) removal, which was mainly originated from its reduction by biochar from Inductively Coupled Plasma Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy. And the corresponding generation of PFRs on biochar was primarily ascribed to the oxidization of phenolic hydroxyl groups by Cr(VI) from Fourier Transform Infrared Spectroscopy analysis, which was further verified by the H₂O₂ treatment experiments. The findings of this study will help to illustrate the transformation of reactive functional groups on biochar and provide a new insight into the role of biochar in environmental remediation.     

大体积水中痕量POPs的联动采集装置及其性能评价

天然水体中的痕量持久性有机污染物(POPs)的定量分析通常需要采集大体积水样.针对大体积水样在过滤和吸附富集过程中滤膜易堵塞且耗时费力的缺点,研制了一种固液分离过滤-吸附富集联动装置.该装置主要由粗过滤器、离心分离屏、倒置微孔过滤器、固相吸附柱、流速控制阀和真空泵组成.与传统的滤膜过滤方式相比,其过滤效率提高了约1.5...     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

Das neue Chemikalienprogramm von UNEP Chemicals

Zusammenfassung  UNEP International Register of Potentially Toxic Chemicals (IRPTC) wurde von der ersten VN-Umweltkonferenz 1972 geschaffen. Sein Einfu? und Zusammenwirken in den 80ziger Jahren mit anderen internationalen Programmen der WHO, FAO, OECD und EG in der Chemikalienkontrolle wird beschrieben. Nach dem Erdgipfel von Rio 1992 werden im VN-Rahmen drei neue Gremien gebildet, die das Fachprogramm des Kapitels 19 der Agenda 21 (umweltfreundliches Chemikalienmanagement) umsetzen sollen: die United nations Commission of Sustainable Development, das Intergovernmental Forum on Chemical Safety und das Interorganization Programme for the Sound Management of Chemicals. Der Erdgipfel brachte auch für IRPTC eine Neuorientierung. Seit 1996 hat UNEP Chemicals, wie sich IRPTC nunmehr nennt, drei Aufgaben in sein Arbeitsprogramm aufgenommen, die beschrieben werden: das internationale übereinkommen zum Prior Informed Consent, das internationale übereinkommen zur Kontrolle der Persistent Organic Pollutants, und schlie?lich sein traditionelles Arbeitsgebiet des Informations-austausches über Stoffe wird weitergeführt.

---

Die Aussagen dieses Beitrages sind die Meinung des Autors. Sie müssen nicht mit der Auffassung des Umweitbundesamtes oder von UNEP Chemicals übereinstimmen.     

Post-war levels of persistent organic pollutants (POPs) in air from Serbia determined by active and passive sampling methods

For the duration of the war accident in former Yugoslavia, several industrial and military targets were burnt and damaged, resulting in a significant release of persistent organic pollutants. Locations heavily targeted in the attacks were later defined by UNEP as four “hot spots”: Kragujevac, Novi Sad, Pancevo and Bor. We analyzed concentration levels of pollutants collected in 2004 and 2005 in air samples from the city of Kragujevac, Serbia, following the war accident of 1999. Pollutants included polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), dichloro-diphenyl-dichloroethane (DDD) and polychlorinated biphenyls (PCBs). We present results obtained during air sampling campaign conducted in July 2004 by the active sampling method; and during September 2004–June 2005 by the passive sampling method. Our findings show the occurrence of residual quantities of DDT, HCH, PCBs and PAHs in air samples. High levels of PCBs are probably due to the destruction of transformers during the war accident.     

重庆市空气污染持续过程特征及其气象成因分析

利用空气质量日报数据分析了重庆市主城区空气质量的总体概况以及持续空气污染过程的特征,并着重探讨了2005年11月29日至12月31日期间的空气污染指数API变化及其与主要气象条件的相关关系.结果显示,一年中主城区出现连续3 d以上空气污染指数API超过100的持续污染过程10次,累计污染超标日为61 d,占全年总超标天数的61.6%;持续污染过程的气象条件往往有着共同的特点,即平均风速小,无降水或降水稀少,大气层结稳定,混合层高度较低.     

Persistent organic pollutants control strategy in China

The development of Persistent Organic Pollutants(POPs) control policy in China in the context of international concerns on POPs was reviewed. The aspects of the Chinese POPs control strategies were analyzed, and compared with those of developed counterparts(e.g. US, EU, Japan). Currently, while the legal framework on POPs management, which complies with intemational guidelines has been established, it should be improved in the areas of special POPs management, risk assessment, the precautionary principle, lifecycle management and technical support capacity. The analysis of Chinese POPs policy and suggestions for strengthening the sciencebased decision making capacity are not only useful for Chinese decision-makers, but also a case study for developing wodd and make a great contribution for the global elimination of POPs to make a toxic-free future.     

Exposure to polycyclic aromatic hydrocarbons and risk for premature ovarian failure and reproductive hormones imbalance

Polycyclic aromatic hydrocarbons (PAHs) are a typical class of persistent organic pollutants that is ubiquitous worldwide. Previous animal studies suggested that PAHs had adverse effects on female reproduction. However, the human data regarding relationship of PAHs exposure with women reproductive health, such as ovarian dysfunction, are scarce. In this case-control study, the associations of serum levels of PAHs with the risk of premature ovarian failure (POF) and reproductive hormones in Chinese women were investigated, with recruiting 157 POF patients and 217 healthy women. The serum levels of 12 types of PAHs, as well as reproductive hormones, including follicle-stimulating hormone, luteinizing hormone and anti-mullerian hormone, were determined. In the logistic regression models, most individual PAH congeners showed significantly positive correlations with the risk of POF (p < 0.05), except for fluorine and pyrene. Benzo(a)pyrene (BaP), as the most carcinogenic PAH congener, was observed to be significantly positively associated with the risk of POF. After adjustment for age, body mass index, educational levels and household income, per one-unit increase in the log-transformed BaP concentration was significantly correlated with 2.191-fold increased risk of POF (OR = 2.191, 95%CI: 1.634–2.938, p < 0.05). To the best of our knowledge, this is the first study to report an association between internal exposure levels of PAHs and the increased risk of POF in women.     

Altitude dependence of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in surface soil from Tibetan Plateau, China

Remote mountain areas besides high latitude regions are beginning to receive increased attention in studying the transport and behavior of persistent organic pollutants (POPs). In the present work, surface soil samples were collected from the Tibetan Plateau, the highest plateau in the world which includes the northern slope of Mt. Qomolangma, to investigate the levels and trends of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) along the altitudinal gradient. The average PCB and PBDE concentrations were 185.6 ng kg⁻¹ dry weight (dw) (range 47.1–422.6 ng kg⁻¹ dw) and 11.1 ng kg⁻¹ dw (range 4.3–34.9 ng kg⁻¹ dw), respectively. Regression analysis between the log-transformed TOC-normalized concentrations and the altitudes of the sampling sites showed two opposite trends with regard to altitude dependence: negative relationship with altitude below about 4500 m followed by a positive altitude dependence above this point. Considering minimum anthropogenic activities and very sparse precipitation in the north of Himalayas, the trends above 4500 m imply that the significant altitude dependence of these two groups of POPs were irrespective of pollution sources, but could be predicted by the global distillation effect involving cold condensation in high altitude mountain areas. Increasing levels of heavier congeners were found in higher altitude sites, although the lighter congeners were the main contributors to the total amount, suggesting that less volatile congeners seem to become enriched easier than those more volatile at higher altitudes in this region.     

Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States

Although the use of the insecticide γ-hexachlorocyclohexane (HCH) is now prohibited in many countries because of its hazardousness, stockpiles of γ-HCH still exist. In this study, we subjected γ-HCH to mechanochemical (MC) treatment with a planetary ball mill in the presence of CaO to investigate the feasibility of using this method for the treatment of γ-HCH stockpiles. We confirmed the degradation of γ-HCH and investigated the degradation mechanism. The major intermediates were identified to be 1,3,4,5,6-pentachlorocyclohexene (γ-PCCH) and chlorobenzenes (CBzs). Analysis of the steric structure of γ-HCH and identification of the degradation intermediates suggested that successive dehydrochlorination led to the formation of trichlorobenzenes. Products of further degradation (dichlorobenzenes, monochlorobenzene, and benzene) were also detected. Surprisingly, methane and ethane were also detected, which suggests cleavage of the C-C bonds of the cyclohexane ring and hydrogenation. All of the chlorine atoms in the γ-HCH could be transformed into inorganic chloride compounds by the MC treatment with CaO. Our results indicate that γ-HCH can be completely dechlorinated by MC treatment.